CN104926850B - The preparation method of Iodotrimethylsilane - Google Patents
The preparation method of Iodotrimethylsilane Download PDFInfo
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- CN104926850B CN104926850B CN201510421040.8A CN201510421040A CN104926850B CN 104926850 B CN104926850 B CN 104926850B CN 201510421040 A CN201510421040 A CN 201510421040A CN 104926850 B CN104926850 B CN 104926850B
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- iodine
- iodotrimethylsilane
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- constant pressure
- hexamethyldisiloxane
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Abstract
The invention provides a kind of preparation method of Iodotrimethylsilane, this preparation method comprises the steps: first to be placed in reaction flask by the hexamethyldisiloxane of superfine aluminium power and half, the hexamethyldisiloxane of iodine and half is placed in constant pressure funnel, reaction system vacuumizes, change nitrogen, three times so repeatedly; Start stirring, be warming up to 60 DEG C, drip the silica-based oxygen ethereal solution of hexamethyl two of iodine; Dropwise, outer temperature is warming up to 130 DEG C of backflows, enters constant pressure funnel and dissolve undissolved iodine in constant pressure funnel after steam is cooled; After iodine all dissolves and is added dropwise to reaction system, then react and react completely for 1-2 hour; Stop heating, be cooled to less than 30 DEG C, change reaction unit into water distilling apparatus, collect main distillate fraction, namely obtain the Iodotrimethylsilane fine work of colourless liquid.
Description
Technical field
The present invention relates to a kind of preparation method of Iodotrimethylsilane, belong to the field of chemical synthesis.
Background technology
Iodotrimethylsilane is widely used at pharmaceutical synthesis and organic synthesis field; in pharmaceutical synthesis, the protection reagent of the functional group such as Iodotrimethylsilane Chang Zuowei hydroxyl, is especially used widely in forth generation cynnematin is as the building-up process of cefepime, cefpirome.Iodotrimethylsilane character is active, and the oxygen in atmosphere easily and in air reacts and goes bad, and limits it and preserves, uses.
The synthetic method of Iodotrimethylsilane has kind more than 10, more practical and be easy to the reaction that industrialized synthetic method is hexamethyldisiloxane and iodine and aluminium powder, and the reaction of hexamethyldisilane and iodine.The Iodotrimethylsilane sold in the market contains a lot of lower boiling impurity (as tetramethylsilane and dimethyl diiodo-silane), and this impure product is unfavorable for the synthesis of cynnematin, also likely forms the side effect after medication.
Application number be 200810018420.7 Chinese invention patent describe a kind of synthetic method of Iodotrimethylsilane, the method with hexamethyldisilane and smart iodine for raw material, reaction generates Iodotrimethylsilane crude product, copper powder is added again by Iodotrimethylsilane crude product, reflux, then distills the Iodotrimethylsilane that can obtain refining.The method purification step, copper powder consumption is large, is unfavorable for the reduction of production cost; Particularly breakneck chemical and the high-risk operation such as need of production sodium Metal 99.5 potassium of hexamethyldisilane, and the price of hexamethyldisilane is far above hexamethyldisiloxane, causes the production cost of the method very high.
Application number be 200610097774.6 Chinese invention patent describe a kind of synthetic method of Iodotrimethylsilane, aluminium powder, hexamethyldisiloxane and iodine first react by the method in a kettle., distillation, obtain Iodotrimethylsilane crude product, again Iodotrimethylsilane crude product is placed in still kettle, adds copper powder, heat up, collect cut, be refining Iodotrimethylsilane.The method yield is low, and the thick yield of reaction only has 84.25%, and refining yield only has 78.49%, and the total recovery namely utilizing the method to prepare Iodotrimethylsilane sterling only has 84.25% × 78.49%=66.13%; Purification step, copper powder consumption is large, is unfavorable for the reduction of production cost.The method operation steps comprises and adds smart iodine in batches, because iodine has higher vapour pressure, easily distils, and irritant smell, easily sublimates after distillation, toxic and corrodibility, so this step operates both contaminate environment also serious harm operator.Iodine and aluminium powder are all solids, and the reaction of solid and solid is slow and unstable, and the aluminium triiodide solid that iodine and aluminium powder reaction generate covers the surface of iodine and aluminium powder, hinders further reaction, yield in this way very low.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of Iodotrimethylsilane, and this preparation method can obtain highly purified Iodotrimethylsilane, and the method yield is very high, operational safety, production cost are very low.
An object of the present invention is to provide a kind of preparation method of Iodotrimethylsilane, described preparation method is specially: be placed in reaction flask by the hexamethyldisiloxane of superfine aluminium power and half, the hexamethyldisiloxane of iodine and half is placed in constant pressure funnel, reaction system vacuumizes, change rare gas element, three times so repeatedly.Start stirring, be warming up to 60 DEG C, drip the hexamethyldisiloxane solution of iodine.Dropwise, outer temperature is warming up to 130 DEG C of backflows, enters constant pressure funnel and dissolve undissolved iodine in constant pressure funnel after steam is cooled.After iodine all dissolves and is added dropwise to reaction system, find that reaction reacts completely for 1-2 hour.Stop heating, be cooled to less than 30 DEG C, change reaction unit into water distilling apparatus, collect main distillate fraction, namely obtain the Iodotrimethylsilane fine work of colourless liquid, described superfine aluminium power is the aluminium powder of more than granularity 300 order.
In a preferred embodiment of the invention, the molar ratio of hexamethyldisiloxane, iodine and aluminium powder is 1:1.5:1.1 ~ 2; Be preferably 1:1.5:1.6 further.
In another preferred embodiment of the present invention, described superfine aluminium power is the aluminium powder between 325 order ~ 800 orders.
In another preferred embodiment of the present invention, described rare gas element is nitrogen.
Equation of the present invention is as follows:
2(CH
3)
3SiOSi(CH
3)
3+3I
2+2Al→4(CH
3)
3SiI+2AlOI
Reaction mechanism of the present invention is as follows:
2Al+3I
2→2AlI
3
2(CH
3)
3SiOSi(CH
3)
3+2AlI
3→2(CH
3)
3SiI+[(CH
3)
3SiOAlI
2]
2
[(CH
3)
3SiOAlI
2]
2→2(CH
3)
3SiI+2AlOi
In the present invention,
One of innovative point of the present invention: in Iodotrimethylsilane molecule, SiI key is very weak, causes it to be easily fuming in atmosphere variable color, so reaction system is nitrogen.
Innovative point two of the present invention: initiated dissolving in system and added iodine, all solid iodines add constant pressure addition in advance, dissolving iodine with the silica-based oxygen ether of raw material hexamethyl two and product Iodotrimethylsilane is added drop-wise in reaction flask with iodine solution, such operation ensures that iodine is free from environmental pollution and does not also endanger operator, and speed of response is fast, yield is high, avoids all shortcomings in batches adding iodine of document.
Innovative point three of the present invention: adopt superfine aluminium power first, find that speed of response is very fast, and reaction is very thorough, reaction yield is far away higher than common aluminium powder; And Late Cambrian: aluminium powder is thinner, and speed of response is faster, and yield is higher.
Innovative point four of the present invention: expensive iodine is inexcessive, and cheap aluminium powder is excessive, and the Iodotrimethylsilane of generation need not be refined, straight run distillation, and purity is just up to 99.3%.
Embodiment
Further will illustrate the present invention below.It is pointed out that following explanation is only illustrating the technical scheme that application claims is protected, any restriction not to these technical schemes.The content that protection scope of the present invention is recorded with appended claims is as the criterion.
Embodiment 1:
Superfine aluminium power (325 order) 8.6g is added, hexamethyl two silica-based oxygen ether 16.2g in 250mL four-hole bottle.One deck rectifying column filler glass spring is first added in constant pressure funnel, then iodine 76.2g and hexamethyl two silica-based oxygen ether 16.2g, reaction system vacuumizes, and changes nitrogen, three times so repeatedly.Start stirring, be warming up to 60 DEG C, drip the silica-based oxygen ethereal solution of hexamethyl two of iodine.Dropwise, outer temperature is warming up to 130 DEG C of backflows, enters constant pressure funnel and dissolve undissolved iodine in constant pressure funnel after steam is cooled.After iodine all dissolves and is added dropwise to reaction system, then react and react completely for 1.5 hours.Stop heating, be cooled to less than 30 DEG C, change reaction unit into water distilling apparatus, collect main distillate fraction 104 ?106 DEG C, obtain 77.3g colourless liquid, yield 96.6%, the purity of Iodotrimethylsilane is 99.3%.
Distill complete, be cooled to 140 DEG C, add 80mL p-Xylol, be cooled to about 60 DEG C, add the aqueous sodium hydroxide solution of 20%, measure solution pH value and regulate PH=6, have a large amount of white precipitate to produce, filter to obtain white aluminium-hydroxide powder, the rate of recovery is close to quantitative.
By filtrate separatory, under condition of ice bath aqueous phase with the vitriol oil regulate PH=1 ?2.Stir the hydrogen peroxide of lower slowly dropping 30%.Leave standstill, layering.Upper strata is for connecing subdiaphanous water layer, and lower floor is the iodine be precipitated out.Suction filtration obtains fine particle shape iodine, dry, and the rate of recovery is close to quantitative.
Embodiment 2:
Superfine aluminium power (800 order) 8.6g is added, hexamethyl two silica-based oxygen ether 16.2g in 250mL four-hole bottle.One deck rectifying column filler glass spring is first added in constant pressure funnel, then iodine 76.2g and hexamethyl two silica-based oxygen ether 16.2g, reaction system vacuumizes, and changes nitrogen, three times so repeatedly.Start stirring, be warming up to 60 DEG C, drip the silica-based oxygen ethereal solution of hexamethyl two of iodine.Dropwise, outer temperature is warming up to 130 DEG C of backflows, enters constant pressure funnel and dissolve undissolved iodine in constant pressure funnel after steam is cooled.After iodine all dissolves and is added dropwise to reaction system, then react and react completely for 1 hour.Stop heating, be cooled to less than 30 DEG C, change reaction unit into water distilling apparatus, collect main distillate fraction 104 ?106 DEG C, obtain 79.6g colourless liquid, yield 99.5%, the purity of Iodotrimethylsilane is 99.6%.
The recovery of aluminium hydroxide and thick iodine is with embodiment 1.
Embodiment 3:
Common aluminium powder (40 order) 8.6g is added, hexamethyl two silica-based oxygen ether 16.2g in 250mL four-hole bottle.One deck rectifying column filler glass spring is first added in constant pressure funnel, then iodine 76.2g and hexamethyl two silica-based oxygen ether 16.2g, reaction system vacuumizes, and changes nitrogen, three times so repeatedly.Start stirring, be warming up to 60 DEG C, drip the silica-based oxygen ethereal solution of hexamethyl two of iodine.Dropwise, outer temperature is warming up to 130 DEG C of backflows, enters constant pressure funnel and dissolve undissolved iodine in constant pressure funnel after steam is cooled.After iodine all dissolves and is added dropwise to reaction system, then react and react completely for 3 hours.Stop heating, be cooled to less than 30 DEG C, change reaction unit into water distilling apparatus, collect containing product Iodotrimethylsilane cut 100 ?150 DEG C, obtain 64.9g red liquid, yield 81.2%, the purity of Iodotrimethylsilane is 83.3%.
The recovery of aluminium hydroxide and thick iodine is with embodiment 1.
Embodiment 4:
Add common aluminium powder (40 order) 8.6g in 250mL four-hole bottle, hexamethyl two silica-based oxygen ether 32.4g, starts stirring, is warming up to 60 DEG C, add iodine 76.2g in batches, and outer temperature is warming up to 140 DEG C of backflows, then reacts and react completely for 4 hours.Stop heating, be cooled to less than 30 DEG C, change reaction unit into water distilling apparatus, collect containing product Iodotrimethylsilane cut 100 ?150 DEG C, obtain 59.4g red liquid, yield 74.2%, the purity of Iodotrimethylsilane is 73.3%.
The recovery of aluminium hydroxide and thick iodine is with embodiment 1.
Embodiment 5:
Add superfine aluminium power (800 order) 8.6g in 250mL four-hole bottle, hexamethyl two silica-based oxygen ether 32.4g, starts stirring, is warming up to 60 DEG C, add iodine 76.2g in batches, and outer temperature is warming up to 140 DEG C of backflows, then reacts and react completely for 4 hours.Stop heating, be cooled to less than 30 DEG C, change reaction unit into water distilling apparatus, collect containing product Iodotrimethylsilane cut 100 ?150 DEG C, obtain 65.7g red liquid, yield 82.1%, the purity of Iodotrimethylsilane is 78.2%.
The recovery of aluminium hydroxide and thick iodine is with embodiment 1.
Embodiment 6:
Superfine aluminium power (200 order) 8.6g is added, hexamethyl two silica-based oxygen ether 16.2g in 250mL four-hole bottle.One deck rectifying column filler glass spring is first added in constant pressure funnel, then iodine 76.2g and hexamethyl two silica-based oxygen ether 16.2g, reaction system vacuumizes, and changes nitrogen, three times so repeatedly.Start stirring, be warming up to 60 DEG C, drip the silica-based oxygen ethereal solution of hexamethyl two of iodine.Dropwise, outer temperature is warming up to 130 DEG C of backflows, enters constant pressure funnel and dissolve undissolved iodine in constant pressure funnel after steam is cooled.After iodine all dissolves and is added dropwise to reaction system, then react and react completely for 1 hour.Stop heating, be cooled to less than 30 DEG C, change reaction unit into water distilling apparatus, collect main distillate fraction 104 ?106 DEG C, obtain 71.5g colourless liquid, yield 89.4%, the purity of Iodotrimethylsilane is 92.4%.
The recovery of aluminium hydroxide and thick iodine is with embodiment 1.
Embodiment 7:
Superfine aluminium power (1000 order) 8.6g is added, hexamethyl two silica-based oxygen ether 16.2g in 250mL four-hole bottle.One deck rectifying column filler glass spring is first added in constant pressure funnel, then iodine 76.2g and hexamethyl two silica-based oxygen ether 16.2g, reaction system vacuumizes, and changes nitrogen, three times so repeatedly.Start stirring, be warming up to 60 DEG C, drip the silica-based oxygen ethereal solution of hexamethyl two of iodine.Dropwise, outer temperature is warming up to 130 DEG C of backflows, enters constant pressure funnel and dissolve undissolved iodine in constant pressure funnel after steam is cooled.After iodine all dissolves and is added dropwise to reaction system, then react and react completely for 1 hour.Stop heating, be cooled to less than 30 DEG C, change reaction unit into water distilling apparatus, collect main distillate fraction 104 ?106 DEG C, obtain 70.1g colourless liquid, yield 87.6%, the purity of Iodotrimethylsilane is 97.6%.
The recovery of aluminium hydroxide and thick iodine is with embodiment 1.
Claims (5)
1. the preparation method of an Iodotrimethylsilane, it is characterized in that: described preparation method is specially: the hexamethyldisiloxane of superfine aluminium power and half is placed in reaction flask, the hexamethyldisiloxane of iodine and half is placed in constant pressure funnel, reaction system vacuumizes, change rare gas element, three times so repeatedly; Start stirring, be warming up to 60 DEG C, drip the hexamethyldisiloxane solution of iodine; Dropwise, outer temperature is warming up to 130 DEG C of backflows, enters constant pressure funnel and dissolve undissolved iodine in constant pressure funnel after steam is cooled; After iodine all dissolves and is added dropwise to reaction system, find that reaction reacts completely for 1-2 hour; Stop heating, be cooled to less than 30 DEG C, change reaction unit into water distilling apparatus, collect main distillate fraction, namely obtain the Iodotrimethylsilane fine work of colourless liquid, described superfine aluminium power is the aluminium powder of granularity more than 300 orders.
2. the preparation method of Iodotrimethylsilane according to claim 1, it is characterized in that, the molar ratio of hexamethyldisiloxane, iodine and aluminium powder is 1:1.5:1.1 ~ 2.
3. the preparation method of Iodotrimethylsilane according to claim 1, it is characterized in that, described rare gas element is nitrogen.
4. the preparation method of Iodotrimethylsilane according to claim 2, it is characterized in that, the molar ratio of hexamethyldisiloxane, iodine and aluminium powder is 1:1.5:1.6.
5. the preparation method of Iodotrimethylsilane according to claim 1, is characterized in that described superfine aluminium power be granularity is 325 order ~ 800 orders.
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Address after: 262725 200m north of the intersection of Xinhai road and Dajiu Road, marine chemical park, Hou Town, Shouguang City, Weifang City, Shandong Province Patentee after: Shandong Boyuan Pharmaceutical Chemical Co.,Ltd. Address before: 262725 Xinsha Road North, 500m west of Dajiu Road, Houzhen project area, Shouguang City, Weifang City, Shandong Province Patentee before: Shandong Boyuan Pharmaceutical Chemical Co.,Ltd. |
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